Amides of ethylene diamine tetra acetic acid



United States Patent O rm. (:1. COM 1/04 US. Cl. 26097.5 3 Claims ABSTRACT OF THE DISCLOSURE Liquid hydrocarbon compositions are provided containing, in an amount sufficient to impart anti-static properties, amides of ethylene diamine tetra acetic acid.

CROSS REFERENCE TO RELATED APPLICATIONS This application is a division of my copending application Ser. No. 710,664, filed Mar. 5, 1968, now Pat. No. 3,455,665.

BACKGROUND OF THE INVENTION Field of the invention This invention relates to organic liquids having desirable anti-static properties, and, in one of its aspects, relates more particularly to organic liquid compositions in the form of volatile organic liquids such as hydrocarbon fuels or solvents which possess low electrical conductivity which, when they accumulate electrostatic charges, may give rise to the hazards of ignition or explosion. Still more particularly in this aspect, the invention relates to the improvement of such organic liquids by incorporating therein, additives which are effectve in increasing the electrical conductivity of such liquids to the extent that accumulation of electrostatic charges, with attendant danger of ignition or explosion, is significantly minimized, particularly in the handling, transportation or treatment of such liquids.

Description of the prior art Prior to the present invention, the low electrical conductivity of many volatile organic liquid compositions has presented the problem of controlling static buildup, particularly during handling and transportation, for the purpose of insuring safe and effective distribution without the concomitant danger of ignition or explosion. For example, volatile organic liquids such as hydrocarbon fuel oils (e.g., gasoline, jet fuels, turbine fuels and the like), or light hydrocarbon oils employed for such purposes as solvents or cleaning fluids for textiles, possess a very low degree of electrical conductivity. In the use of such fluids, electrostatic charges, which may be generated by handling, operation or other means, tend to form on the surface, and may result in sparks, thus resulting in ignition or explosion. These hazards may be encountered merely in the handling or transportation of such organic liquids and even in operations, such as centrifuging, in which a solid is separated from a volatile liquid, during which electrostatic charges can accumulate.

Various materials have heretofore been proposed for incorporation into such organic liquid compositions for increasing their electrical conductivity and thus reduce the aforementioned dangers of ignition and explosion. Such materials, however, have not been proved to be sufficiently effective in increasing the desired electrical conductivity of these fluids and, in many instances, have been found to be too costly for the relatively small degree of increased protection which they are capable of providing.

SUMMARY or THE INVENTION In accordance with the present invention, improved liquid hydrocarbon compositions are provided containing, in an amount sufiicient to impart anti-static properties, amides of ethylene diamine tetra acetic acid. The incorporation of these anti-static agents in the liquid compositions, imparts increasedelectrical conductivity to an extent greater than that which has heretofore been realized with many other anti-static materials.

In general, the present invention, in its preferred applications, contemplates organic liquid compositions which normally are capable of accumulating a relatively large degree of electrostatic charge, resulting in the aforementioned hazards of ignition and explosion, having incorporated therein a small amount of the aforementioned amides, usually from about 1 to about 200, and preferably from about 5 to about 50 pounds per thousand barrels of the total volume of the liquid composition.

A field of specific applicability of the present invention is in the improvement of organic liquid compositions in the form of petroleum dstillate fuel oils having an initial boiling point from about F. to about F. and an end boiling point from about 250 F. to about 1000 F. It should be noted, in this respect, that the term distillate fuel oils" is not intended to be restricted to straight-run distillate fractions. These distillate fuel oils can be straightrun distillate fuel oils, catalytically or thermally cracked (including hydrocracked) distillate fuel oils or mixtures of straight-run distillate fuel oils, naphthas and the like, with cracked distillate stocks. Moreover, such fuel oils can be treated in accordance with well known commercial methods, such as acids or caustictreatment, hydrogenation, solvent refining, clay treatment, and the like.

The distillate fuel oils are characterized by their relatively low viscosity, pour point and the like. The principal property which characterizes these contemplated hydrocarbons, however, is their distillation range. As hereinbefore indicated, this range will lie between about 75 F. and about 1000 F. Obviously, the distillation range of each individual fuel oil will cover a narrower boiling range, falling nevertheless, within the above-specified limits. Likewise, each fuel oil will boil substantially, continuously, throughout its distillation range.

Particularly contemplated among the fuel oils are Nos. 1, 2 and 3 fuel oils, used in heating and as diesel fuel oils, gasoline, turbine fuels and the jet combustion fuels, as previously indicated. The domestic fuel oils generally conform to the specifications set forth in ASTM specification D39648T. Specifications for diesel fuels are defined in ASTM specification D975-48TjTypical jet fuels are defined in military specification MIL-F5624B.

The novel anti-static agents of the present invention may comprise any amide of ethylene diamine tetra acetic acid. Particularly preferred, and representative of such amides, are the tetra Primene 81R amide of ethylene diamine tetra acetic acid; the tetra Primene JMT amide of ethylene diamine tetra acetic acid; the tetra N-soya, 1,3- propylene diamine amide of ethylene diamine tetra acetic acid; and the tetra amide obtained by reacting 4 mols of the condensation product of 1 mole of oleyl diamine and 1 mol of a tall oil fatty acid, with 1 mol of ethylene diamine tetra acetic acid. It will be understood, of course, that other amides of the aforementioned type may also be successfully incorporated into organic liquid compositions for their beneficial anti-static effect.

DESCRIPTION OF SPECIFIC EMBODIMENTS The following examples will serve to illustrate the preparation of the novel anti-static agents of the present invention, and the affect thereof when these agents are present in organic liquid compositions for the purpose of 3 effectively imparting anti-static properties thereto, and particularly with respect to liquid hydrocarbon fuels.

Example 1 200 grams (1 mol) of Primene 81R 1 was stirred with 73 grams (0.25 mol) of ethylene diamine tetra acetic acid at a temperature of 205 C. until evolution of water had ceased. The product thus formed was found to be the tetra Primene 81R amide of ethylene diamine tetra acetic acid.

Example 2 300 grams (1 mole) of Primene J MT 2 was stirred with 72 grams (0.25 mol) of ethylene diamine tetra acetic acid at a temperature of 205 C. until evolution of Water had ceased. The product thus formed was found to be the tetra Primene J MT amide of ethylene diamine tetra acetic acid.

Example 3 310 grams (0.82 mol) of N-soya 1,3-propylene diamine was stirred with 60 grams (0.205 mol) of ethylene diamine tetra acetic acid at a temperature of 200 C. until evolution of water had ceased. The product thus formed was found to be tetra N-soya 1,3-propylene diamine amide of ethylene diamine tetra acetic acid.

Example 4 320 grams (0.584 mol) of the condensation product of one mol of oleyl diamine and one mol of a mixture of tall oil fatty acids at 300 C. and 40 grams (0.146 mol) of ethylene diamine tetra acetic acid were stirred at a temperature of 285 C. until evolution of water had ceased. The product thus formed was found to be the corresponding tetra amide of the aforementioned condensation product and the ethylene diamine tetra acetic acid.

In accordance with the data of the following table a series of comparative electrical conductivity tests were carried out for the purpose of determining the aforementioned properties of the compositions prepared in accordance with Examples 1 through 4 with respect to imparting anti-static properties to organic liquid compositions. The test employed for this purpose was electrical conductivity measured in picomhos (i.e., -12 mhos) per meter. In these tests the aforementioned antistatic agents were blended in a liquid hydrocarbon fuel composition comprising about 75% catalytically cracked component and about 25% straight-run component, boiling at a temperature from about 320720 F. The resulting fuel compositions were then evaluated for their degree of improvement in electrical conductivity with the results shown in the table.

A mixture of primary amines having a tertiary carbon atom attached to the amino (-NH2) group, containing from about 12 to about 15 carbon atoms per amine molecule.

A mixture of primary amines having a tertiary carbon atom attached to the amino NH2) group containing from about 18 to about 24 carbon atoms per amine molecule,

As will be seen from the data of the examples of the foregoing table a marked improvement in anti-static properties of organic liquid compositions is obtained through the use of the anti-static additives of the present invention. It will be understood, of course, that the improved organic liquid compositions of the present invention may, if so desired, contain various other additives or mixtures of such additional additives in order to further enhance their properties. Thus, the organic liquid compositions of the present invention may also contain such additives as antioxidants, detergents, dispersants, stability improvers and the like. It will also be understood that although the present invention has been described with preferred embodiments, various modifications and adaptations thereof may be resorted to without departing from the spirit and scope of the invention, as those skilled in the art Will readily understand.

I claim:

1. An amide selected from the group consisting of the tetra N-soya 1,3-propylene diamine amide of ethylene diamine tetra acetic acid and the tetra amide obtained by reacting 4 mols of the condensation product of 1 mol of oleyl diamine and 1 mol of a tall oil fatty acid with 1 mol of ethylene diamine tetra acetic acid.

2. The amide of claim 1 wherein said amide comprises the tetra N-soya 1,3-propylene diamine amide of ethylene diamine tetra acetic acid.

3. The amide of claim 1 wherein said amide comprises the tetra amide obtained by reacting 4 mols of the condensation product of 1 mol of oleyl diamine and 1 mol of a tall oil fatty acid, with 1 mol of ethylene diamine tetra acetic acid.

References Cited UNITED STATES PATENTS 3,173,770 3/1965 Thompson et al. 4471 3,202,491 8/1965 Maxwell 44-71 FOREIGN PATENTS 704,931 3/1965 Canada 44-71 DONALD E. CZAJA, Primary Examiner WILLIAM E. PARKER, Assistant Examiner U.S. c1. X.R.

@33 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,5 7, 7 Dated m r 5, 97

Inventor(s) H rry J. Andress, Jr.

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 7, for "compositions" read --composition-- Column 2, line 21, for dstillate" read --distillate-- Column 2, line 32, for "acids" read -acid-- Column 3, line 12, for "72" read --73-- Signed and sealed this 30th day of November 1971.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. RCBER'I GOTTSCHALK Attesting Officer Acting Commissioner of Pete 

